US3012029A - 3, 6-dioxygenated 17alpha-(2-carboxyethyl)-androstane-5alpha, 17beta-diol lactones - Google Patents
3, 6-dioxygenated 17alpha-(2-carboxyethyl)-androstane-5alpha, 17beta-diol lactones Download PDFInfo
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- US3012029A US3012029A US26941A US2694160A US3012029A US 3012029 A US3012029 A US 3012029A US 26941 A US26941 A US 26941A US 2694160 A US2694160 A US 2694160A US 3012029 A US3012029 A US 3012029A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J21/00—Normal steroids containing carbon, hydrogen, halogen or oxygen having an oxygen-containing hetero ring spiro-condensed with the cyclopenta(a)hydrophenanthrene skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J75/00—Processes for the preparation of steroids in general
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- This invention relates to 3,5,6-trioxygenated 17a-(2- carboxyethyl)androstan-175-ol lactones and processes for the manufacture thereof. More particularly, this invention relates to chemical compounds of the formula in which R represents an alkyl radical containing fewer than 9 carbon atoms, to wit, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, tert-pentyl, neopentyl, hexyl, isohexyl, heptyl, octyl, and isomeric C H groupings.
- the alkoxymethylidyne radicals represented by Y and the alkoxymethylene radicals represented by Z likewise are preferably of lower order, such radicals being comprehended by the formulas respectively, R in the latter two formulas having the meaning previously assigned.
- the foregoing radicals are so disposed in the steroid nucleus of the subject lactones that the hydroxy and alkanoyloxy groupings within the ambit of X, and the hydroxy, alkanoyloxy, and alkoxy groupings embraced by Z, are in the ,9 configuration, whereas the hydroxy and alkoxy groupings called for by Y are tat-oriented.
- other stereochemical arrangements of these Equivalent to the described lactones for purposes of the'present invention are corresponding hydroxy acids and their alkali salts, of the formula CHzGHzCO OM.
- X, Y, and Z have the same meanings as above and represents hydrogen, an alkali metal, or the ammonium radical.
- the compounds to which this invention relates are useful because of their valuable pharmacological properties.
- they are potent diuretics, being adapted to block the effect of desoxycorticosterone acetate on urinary sodium and potassium.
- Example 1 1 7 a- (Z-carboxyethyl andr0stane-3 6,5 0:,6 [3,1 7 B-tetraol 'ylactone.-To a solution of 50 parts of l7a-(2-carboxyethyl)-5a,6a-epoxyandrostane-3B,17,3-diol 'y-lactone (US. 2,946,787) in 360 parts of acetone is added a solution of 46 parts of concentrated sulfuric acid in parts of water. The resultant mixture is allowed to remain overnight at room temperatures, then diluted with water to precipitate a paste which solidifies on standing.
- the solid material is filtered off and recrystallized from aqueous methanol to give the desired 17u-(2-carboxyethyl)- androst-ane-3,8,5u,6fi,l7fl-tetraol 'y-lactone melting at 255- 263.5, and further characterized by a specific rotation of --43.
- the product has the formula stan-6-one 'y-lac't0ne.-A mixture of 40 parts of l7u-(2- carboxyethyDandrostane 3/3,5
- the resultant 17a-(2-carboxyethyl)-3B,5a,17,3-trihydroxyandrostan-6-one 'ylactone is characterized by a specific rotation of -82". It has the formula Example 3 1 7 oc-(2-carb0xyefhyl -5 00,1 7fl-dihydr0xyandr0stane-3,6- dione 'y-lact0ne.
- the benzene phase from the partitioning described in Example 2 successively washed with aqueous 5% sodium carbonate and water, affords, on standing, a crystalline precipitate which, recrystallized from a mixture of acetone and hexane, melts at 245 (with decomposition).
- This material is l7a-(2-carboxyethyl)-5a,17fl-dihydroxyan'drostane-3,6-dione 'y-lactone, of
- 17,3 diol' 'y lactone in 400 parts of methanol contain- 4 rial which precipitates on standing is collected on a filter, Washed with water, and finally recrystallized from aqueous methanol. It melts at 176.5179.5, has a specific rotation of -66, and is 17a-(2-carboxyethyl)- 6,8-methoxyandrostane-319,504,17B-triol 'y-lactone, of the formula OCH:
- Example 5 a (2 carboxyethyl) 50:,175 dihydroxy 6,8- methoxyandrostan 3 one 7 lact0ne.
- a solution of approximately 20 parts of 17a-(2-carboxyethyD-65- methoxyandrostane-3B,5a,17,8-triol 'y-lactone in 800 parts of acetone is slowly added a solution of 6 parts of chromic acid in a mixture of approximately 16 parts of water and 9 parts of concentrated sulfunic acid.
- suflicient 2-propanol is introduced to destroy excess chromic acid, whereupon the resultant mixture is diluted With approximately 20 volumes of water.
- the crystalline solid which preoipitates is collected on a filter and recrystallized from aqueous methanol.
- the material thus obtained is l7a- (2 carboxyethyl) 511,175 dihydroxy 6e methoxyandrostan 3 one 7 lactone, melting at approximately 252 (with decomposition) and having a specific rotation of -37.
- the product has the formula (SCH:
- Example 6 3p acetoJty 17a (.2-carboxyethyl)-6,B-meth0xyandrostane-5u,17 8-diol 'y-lactone.-A solution of 1 part of l7a-(2-carboxyethyl) 6/8 'methoxyandrostane 35,501, 17,8-triol 'y-lactone and 1 part of acetic anhydride in 10 parts of pyridine is let stand at room temperatures overnight, then diluted with 20 volumes of water. The resultant mixture is extracted with ether. The ether extract is washed with water and then freed of solvent by distillation, whereupon the residue is dried azeotropically by the distillation of benzene therefrom.
- the residue is 17u-(2-carb0xyethyl)-5u,6 3,17fl-trihydroxya'ndrost'an-one 'y-1actone,'of the formula wherein X represents a member of the group consisting of carbonyl, B-hydroxymethylene, and [i-[Uower alkanoyl)oxy]methylene radicals; and Z represents a member of the group consisting of carbonyl, B-hydroxymethylene, fi-methoxymethylene, and fi-[(lower a1kanoyl)- oxylmethylene radicals.
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Description
groupings are of course contemplated.
United States Patent 3,012,029 3,6-DIGXYGENATED 17a-(2-CARBOXYETHYL)- ANDROSTANE-5a,17}3-DIOL LACTONES Roy H. Bible, J12, Morton Grove, 11]., assignor to G. D. Searle & Co., Chicago, 111., a corporation of Delaware No Drawing. Filed May 5, 1960, Ser. No. 26,941 9 Claims. (Cl. 260239.57)
This invention relates to 3,5,6-trioxygenated 17a-(2- carboxyethyl)androstan-175-ol lactones and processes for the manufacture thereof. More particularly, this invention relates to chemical compounds of the formula in which R represents an alkyl radical containing fewer than 9 carbon atoms, to wit, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, tert-pentyl, neopentyl, hexyl, isohexyl, heptyl, octyl, and isomeric C H groupings. The alkoxymethylidyne radicals represented by Y and the alkoxymethylene radicals represented by Z likewise are preferably of lower order, such radicals being comprehended by the formulas respectively, R in the latter two formulas having the meaning previously assigned.
Optimally, the foregoing radicals are so disposed in the steroid nucleus of the subject lactones that the hydroxy and alkanoyloxy groupings within the ambit of X, and the hydroxy, alkanoyloxy, and alkoxy groupings embraced by Z, are in the ,9 configuration, whereas the hydroxy and alkoxy groupings called for by Y are tat-oriented. However, other stereochemical arrangements of these Equivalent to the described lactones for purposes of the'present invention are corresponding hydroxy acids and their alkali salts, of the formula CHzGHzCO OM.
ice
wherein X, Y, and Z have the same meanings as above and represents hydrogen, an alkali metal, or the ammonium radical. Those skilled in the art will appreciate that the described salts readily derive from the apposite lactones on contact with aqueous alkali. The free acids, in turn, are obtained from the salts by a critically brief exposure to a proton source; prolongation of the exposure time induces lactonization.
The compounds to which this invention relates are useful because of their valuable pharmacological properties. For example, they are potent diuretics, being adapted to block the effect of desoxycorticosterone acetate on urinary sodium and potassium.
The following examples describe in detail compounds illustrative of the present invention and methods which have been devised for their manufacture. However, the invention is not to be construed as limited thereby, either in spirit or in scope, since it will be apparent to those skilled in the art of organic synthesis that many modifications, both of materials and of methods, may be practiced without departing from the purpose and intent of this disclosure. Throughout the examples hereinafter set forth, temperatures are given in degrees centigrade and relative amounts of materials in parts by Weight, except as otherwise noted.
Example 1 1 7 a- (Z-carboxyethyl andr0stane-3 6,5 0:,6 [3,1 7 B-tetraol 'ylactone.-To a solution of 50 parts of l7a-(2-carboxyethyl)-5a,6a-epoxyandrostane-3B,17,3-diol 'y-lactone (US. 2,946,787) in 360 parts of acetone is added a solution of 46 parts of concentrated sulfuric acid in parts of water. The resultant mixture is allowed to remain overnight at room temperatures, then diluted with water to precipitate a paste which solidifies on standing. The solid material is filtered off and recrystallized from aqueous methanol to give the desired 17u-(2-carboxyethyl)- androst-ane-3,8,5u,6fi,l7fl-tetraol 'y-lactone melting at 255- 263.5, and further characterized by a specific rotation of --43. The product has the formula stan-6-one 'y-lac't0ne.-A mixture of 40 parts of l7u-(2- carboxyethyDandrostane 3/3,5|x,6fi,l7fi3 tetraol lactone dissolved in 1350 parts of benzene with 17 parts of chromic acid dissolved in 298 parts of acetic acid and 186 parts of water is agitated during 4 hours at room temperatures. The mixture is then partitioned between water and benzene.
The aqueous phase, combined with washings from work-up of the benzene phase as described in Example 3 hereinafter and allowed to stand, affords a crystalline precipitate of 17a (2 carboxyethyl) 313,504,175 trihydroxyandrostan-S-one 'y-lactone which, washed with water and thereupon recrystallized from methanol, is obt ained as the monomethanolate. This material loses solvent at about 165, melts at 282284, and displays a specific rotation of 78". It can be completely desolvated by heating at around 200 in vacuo for approximately 4 hours. The resultant 17a-(2-carboxyethyl)-3B,5a,17,3-trihydroxyandrostan-6-one 'ylactone is characterized by a specific rotation of -82". It has the formula Example 3 1 7 oc-(2-carb0xyefhyl -5 00,1 7fl-dihydr0xyandr0stane-3,6- dione 'y-lact0ne.The benzene phase from the partitioning described in Example 2, successively washed with aqueous 5% sodium carbonate and water, affords, on standing, a crystalline precipitate which, recrystallized from a mixture of acetone and hexane, melts at 245 (with decomposition). This material is l7a-(2-carboxyethyl)-5a,17fl-dihydroxyan'drostane-3,6-dione 'y-lactone, of
V the formula An alternative procedure for the manufacture of this product consists in slowly adding a solution of approximately 17 parts of chromic acid in a mixture of 45 parts of water and approximately 25 parts of concentrated sulfuric acid to a solution of 40 parts of l7a(2-carboxyethyl)androstane-3fi,5a,6fi,17,3-tetraol -laotone in 1600 parts of acetone. Excess chromic acid is then decomposed by addition of 2-propanol, whereupon the reaction mixture is diluted with water to throw down the desired 17a (2 carboxyethyl)5a,l7;S dihydroxyandrostane- 3,6-dione 'y-lactone as a solid precipitate. The product, collected on a filter and recrystallized from aqueous methanol, manifests a specific rotation of -53.
7 Example 4 17oz (2 carboxyethyl) 65 methoxyandrostane- 35,511,176 trial 7 lact0ne.--A solution of 100 parts of 170: (2 carboxyethyl) 5a,6a epoxyandrostane 35,-
17,3 diol' 'y lactone in 400 parts of methanol contain- 4 rial which precipitates on standing is collected on a filter, Washed with water, and finally recrystallized from aqueous methanol. It melts at 176.5179.5, has a specific rotation of -66, and is 17a-(2-carboxyethyl)- 6,8-methoxyandrostane-319,504,17B-triol 'y-lactone, of the formula OCH:
Example 5 a (2 carboxyethyl) 50:,175 dihydroxy 6,8- methoxyandrostan 3 one 7 lact0ne.To a solution of approximately 20 parts of 17a-(2-carboxyethyD-65- methoxyandrostane-3B,5a,17,8-triol 'y-lactone in 800 parts of acetone is slowly added a solution of 6 parts of chromic acid in a mixture of approximately 16 parts of water and 9 parts of concentrated sulfunic acid. When the addition is complete, suflicient 2-propanol is introduced to destroy excess chromic acid, whereupon the resultant mixture is diluted With approximately 20 volumes of water. The crystalline solid which preoipitates is collected on a filter and recrystallized from aqueous methanol. The material thus obtained is l7a- (2 carboxyethyl) 511,175 dihydroxy 6e methoxyandrostan 3 one 7 lactone, melting at approximately 252 (with decomposition) and having a specific rotation of -37. The product has the formula (SCH:
Example 6 3p acetoJty 17a (.2-carboxyethyl)-6,B-meth0xyandrostane-5u,17 8-diol 'y-lactone.-A solution of 1 part of l7a-(2-carboxyethyl) 6/8 'methoxyandrostane 35,501, 17,8-triol 'y-lactone and 1 part of acetic anhydride in 10 parts of pyridine is let stand at room temperatures overnight, then diluted with 20 volumes of water. The resultant mixture is extracted with ether. The ether extract is washed with water and then freed of solvent by distillation, whereupon the residue is dried azeotropically by the distillation of benzene therefrom. The material thus obtained, recrystallized from a mixture of acetone and hexane, melts at approximately 132-", resolidifies above this temperature, and melts again at approximately 177". This material is S/S-acetoxy- 7a-(2- carboxyethyD-6,8-methoxyandrostane 5a,17fl-dio1 'y-lactone, of the formula Example 8 17a (2- carboxyethyl) 33,613, dipropionyloxyandrostane-a,17fi-diol 'y-lactone.Substitution of '1 part of propionic anhydride for the acetic anhydride -called for in Example 7 affords, by the procedure there detailed, 17a (2 carboxyethyl) 35,65 dipropionyloxyandrostane-5oz ,l7fi-diol 'y-lactone of the formula I CC2H on Example 9 6,8 acetoxy 17a (2 carboxyethyDandrostane- 3B,5a,17fl-tfi0l -lacto'ne.To a solution of 1 part of 3B,6B-diacetoxy-l7a (2-carboxyethyl)androstane-5a,17,3- diol 'y-lactone in approximately 30 parts of methanol is added 4 parts of aqueous sodium hydroxide. The resulting mixture is allowed to stand at room temperatures for 2% hours, then diluted with 18 volumes of water, and finally acidified with 5% hydrochloric acid. The
product which precipitates is the desired 6p-acetoxy-17a- 75 Example ll afiords by the procedure there detailed, 17
(2 carboxyethyDandrostane -'3fi,5a,l7fi-triol 'y-lactone, the formula of which is HaC' Example 10 63 acetoxy 17a (2 carboxyethyl) 50:,1713 dz'hydroxyandrostan 3 one 'y-lact0ne.-Substitution of approximately 45 parts of 6,8-acetoXy-17a-(2-carboxyeth- 'yDandrostane 3 5,5 u,17fi triol 'y-l'actone for the 1704-(2- carboxyethyl)androstane-3,8,5a,6fi,17,8 tetraol 'y-lactone called for in Example 3 (second paragraph) affords, by the procedure there detailed, 6,8-acetoxy-l7u-(2-carboxyethyD-Su,1718-dihydroxyandrostan-3-one 'y-lactone, of the formula Example 11 the formula v v Example 12 17a;-(Z-carboxyezhyl) 3,9 propionyloxyandrostane-j'e, 6,8,17,3-tr ial -lactone.Substitution of 13 parts of propionic anhydride for the acetic anhydride called for in 7 (2carboxyethyl)-3,8-propionyloxyandrostane 5a,6fi,17fitriol y-lactone, of the formula V 3fl-acetoxy 17a-(2-carboxyethyl)-5 z,17,3-dihydroxyandrstan-6-0ne *y-lactona-Substitution of 45 parts of 3B- acetoxy-17a-(Z-carboxyethyl)androstane a,6,B,17fl-trio1 -lactone for the 17a-(Z-carboxyethyl)androstane-3B,5u, 6,3,17,8-tetraol -lactone called for in Example 3 (second paragraph) affords, by the procedure there detailed, 3 6- acetoxy-17a-(Z-carboxyethyl) 5 0:,175 dihydroxyandrostan-6-one -lactone, of the formula Example 14 V A. 6,3-benzyl0xy 17a-(2-carb0xyethyl)androstane-3/3, 50:,1713-2Ii0l 7-lact0ne.-A mixture of parts of '17u-(2- carboxyethyl) -5tX,6tX epoxyand rostane-3,8,l7fi-diol 'y-lactone, parts of benzyl alcohol, 1 part of concentrated sulfuric acid, and 320 parts of acetone-is allowed to stand at room temperatures for 2 days. The reaction mixture is then partitioned between water and ether. The ether phase, upon evaporation of solvent, afiords 6 3-benzyloxy- 170t-(2-carboxyethyl)androstane-3B,5a,l7fl-triol 'y-lactone as the residue.
B. 6j3-benzyloxy 17u-(2 carboxyethyl)-5a,17fl-dihydroxyandroszan-3-one y-lactoneAubstitution of approximately 60 parts of 6;8-benzyloxy-17a-(2-carboxyethyl)- androstane-3B,5a,17/8 triol 'y-lactone for the l7a-(2-carboxyethyl) androstane 35,5a,6;8,l7fl tetraol 'y-lactone called'for in Example 3 (second paragraph) affords, by the procedure there detailed, 6fl-benzyloxy-17a-(2-can i boxyethyl) -5 a, 17 B-dihydroxyandrostan-3 -one 'y-lactone.
C. 17a-(2-carboxyethyl) -5a,6p,17p trihydroxyandrostan-3-one 7-lact0ne;A solution of 4 parts of 6,8-benz'yloxy-17 -(2-carboxyethyl)-5 0:,175 dihydroXyandrostan-Zlone 'y'-1actone in 80 parts of 95%ethanol is agitated at room temperatures under approximately 5 atmospheres 'of hydrogen for 12 hours in the presence of 1 part of 5% r V palladium-on-charcoal. The resultant mixture is filtered, w and the filtrate is'stripped of solvent by vacuum distillation. The residue is 17u-(2-carb0xyethyl)-5u,6 3,17fl-trihydroxya'ndrost'an-one 'y-1actone,'of the formula wherein X represents a member of the group consisting of carbonyl, B-hydroxymethylene, and [i-[Uower alkanoyl)oxy]methylene radicals; and Z represents a member of the group consisting of carbonyl, B-hydroxymethylene, fi-methoxymethylene, and fi-[(lower a1kanoyl)- oxylmethylene radicals.
2. 17a (2 carboxyethyhandrostane 3/3,5a,6;3,17fitetraol 'y-lactone.
3. 17a (2 carboxyethyl) methoxyandrostane- 3;3,5a,17fl-triol 'y-lactone.
4. 17a (2 carboxyethyl) 3B,5a,*17fi trihydroxyandrostan-6-one 'y-lactone.
5. 3B acetoxy 17a (2 carboxyethyl) 6 3 methoxy-androstane-5a,17B-diol 'y-lactone.
6. 17a (2 carboxyethyl) 504,175 dihydroxy 6,8- methoxyandrostan-3-one y-lactone.
7. 17a (2 carboxy'ethyl) 5.1,175 dihydroxy androstane-3,6-dione 'y-lactone.
8. A compound of the formula 9. A compound of the formula lower alkyl-fi-O V O l
Claims (1)
1. A COMPOUND OF THE FORMULA
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| Application Number | Priority Date | Filing Date | Title |
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| US26941A US3012029A (en) | 1960-05-05 | 1960-05-05 | 3, 6-dioxygenated 17alpha-(2-carboxyethyl)-androstane-5alpha, 17beta-diol lactones |
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| US26941A US3012029A (en) | 1960-05-05 | 1960-05-05 | 3, 6-dioxygenated 17alpha-(2-carboxyethyl)-androstane-5alpha, 17beta-diol lactones |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3086031A (en) * | 1960-10-28 | 1963-04-16 | American Cyanamid Co | Substituted steroid ethers of the pregnane series |
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1960
- 1960-05-05 US US26941A patent/US3012029A/en not_active Expired - Lifetime
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3086031A (en) * | 1960-10-28 | 1963-04-16 | American Cyanamid Co | Substituted steroid ethers of the pregnane series |
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